Presence of Jahn-Teller distortions in a novel six-coordinate Ag(II) complex: temperature dependent EPR,optical and magnetic susceptibility measurements

Single-crystal variable temperature EPR, optical and polycrystalline magnetic susceptibility studies have been made on a novel six-coordinate Ag(II) complex. Temperature dependent EPR studies on pure single crystals of this compound reveal that dynamic Jahn-Teller distortion operates above 230 K, between 230 K and 120K static Jahn-Teller distortion sets in and below 110 K there is evidence of exchange interaction. Crystal g values were obtained by least-squares fitting with the data obtained from the orientation dependent EPR spectra of the undiluted single crystal of this complex at 300 K and 77 K. From an optical study the Jahn-Teller stabilization energy is found to be ～2250cm^?1. Comparison of Abs_max values for other silver(II) compounds enables us to conclude that the formal geometry of this complex is a tetragonally distorted octahedral. Infrared spectra of this complex were also recorded over a wide range of temperature. Magnetic susceptibility measurements over a wide range of temperature on the powder sample of this compound reveal that the complex is antiferromagnetically coupled in the temperature range 5–40 K with 2J = 0.906cm^?1, and above 40K it is ferromagnetically coupled with 2J = +7.4cm^?1. The effective magnetic moment (μ_eff) of this complex has been compared with that of a series of other silver(II) complexes available in the literature. Finally, the spectral and magnetic data of this complex have been compared with those of a corresponding isostructural and isomorphous copper(II) complex.     

Intramolecular Dynamics of the 1,2,4-Trifluorobenzene Radical Anion: An Optically Detected EPR and Quantum Chemistry Study

A previously unknown electron paramagnetic resonance (EPR) spectrum of the 1,2,4-trifluorobenzene radical anion in liquid solution in nonpolar solvent has been obtained by means of the optically detected EPR technique. On the basis of quantum chemical calculations, the observed fluorine hyperfine coupling values and their temperature dependence have been interpreted as a consequence of fast conformational exchange among different nonplanar structures.     

Magnetic resonance of spin clusters and triplet excitations in a spin-Peierls magnet with impurities

The magnetic resonance spectrum of spin clusters formed in spin-Peierls magnets in the vicinity of impurity ions is investigated. The observed temperature dependences of the effective g-factor and the linewidth of the electron paramagnetic resonance (EPR) in crystals of Cu_1?x Ni_xGeO₃ are described in the model of the exchange narrowing of the two-component spectrum with one component ascribed to spin clusters and exhibiting an anomalous value of the g-factor and the other related to triplet excitations. An estimation of the size of the suppressed dimerization region around the impurity ion is obtained (this region includes about 30 copper ions). The dependence of the effective g-factor and the EPR linewidth on the impurity concentration at low temperatures indicates the interaction of clusters.     

磁场和温度对束缚磁极化子有效质量的影响

研究强、弱耦合情形下,库仑场中束缚磁极化子的性质.采用改进的线性组合算符方法研究束缚磁极化子的振动频率和有效质量的温度依赖性,对RbCl晶体进行数值计算,结果表明:在强耦合情形下,束缚磁极化子的振动频率随温度的升高和磁场的增强而增加;有效质量随温度的增加而增加,但随磁场的增强而减少.     

Manifestations in the EPR spectrum shape of memory effects in the electron spin polarization in the case of two consecutive radical pairs

Electron paramagnetic resonance (EPR) spectra of two consecutive radical pairs (RPs) diffusing inside micelles are numerically calculated. Calculations are carried out for various values of the micelle radius, exchange integral, and mutual diffusion coefficient. In the simple case when the hyperfine interaction with magnetic nuclei can be neglected, it is demonstrated that the spin dynamics in the primary radical pair (RP1) manifests itself in the EPR spectrum of the secondary radical pair (RP2) in a characteristic way: the oddness of the EPR spectrum with respect to its center is violated, and the EPR line intensities and widths for the two partners in the RP2 differ. These features of the RP2 EPR spectrum shape are interpreted as follows: the spin dynamics in the RP1 produces a longitudinal spin polarization and a transverse spin polarization (i.e., spin coherence). Both polarizations are transferred from RP1 to RP2. This spin polarization transfer causes the above features of the RP2 EPR spectrum shape. It is shown that the RP2 EPR spectrum in a sequence of RPs cannot be simulated as a spectrum of a single RP. The features of the RP2 EPR spectrum shape may be, in principle, exploited to reveal the existence of the short-lived RP1.     

Magnetic and EPR studies of the EuFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystal

Magnetic and electron paramagnetic resonance (EPR) properties of EuFe₃(BO₃)₄ single crystals have been studied over the temperature range of 300–4.2 K and in a magnetic field up to 5 T. The temperature, field and orientation dependences of susceptibility, magnetization and EPR spectra are presented. An antiferromagnetic ordering of the Fe subsystem occurs at about 37 K. The easy direction of magnetization perpendicular to the c axis is determined by magnetic measurements. Below 10 K, we observe an increase of susceptibility connected with the polarization of the Eu sublattice by an effective exchange field of the ordered Fe magnetic subsystem. In a magnetic field perpendicular to the c axis, we have observed an increase of magnetization at T < 10 K in the applied magnetic field, which can be attributed to the appearance of the magnetic moment induced by the magnetic field applied in the basal plane. According to EPR measurements, the distance between the maximum and minimum of derivative of absorption line of the Lorentz type is equal to 319 Gs. The anisotropy of g-factor and linewidth is due to the influence of crystalline field of trigonal symmetry. The peculiarities of temperature dependence of both intensity and linewidth are caused by the influence of excited states of europium ion (Eu³⁺). It is supposed that the difference between the g-factors from EPR and the magnetic measurements is caused by exchange interaction between rare earth and Fe subsystems via anomalous Zeeman effect.     

Anisotropic exchange interactions in CuTe2O5

Electron paramagnetic resonance (EPR) was used to study CuTe₂O₅ single crystals at frequencies of 9.4 and 160 GHz. Analytic expressions for the second and fourth moments of the EPR line are deduced with inclusion of the difference between the exchange couplings of the copper spin with its different neighbors. From comparing the calculated and measured EPR linewidths, the positions of copper ions with the strongest exchange interactions are identified. The parameters of the anisotropic exchange interaction between copper ions in a pair are found. The parameter of the exchange interaction between magnetically nonequivalent copper centers is determined from the frequency dependence of the EPR linewidth. The directions of the principal axes of the g tensors are established. The data obtained count in favor of a quasi-one-dimensional model of magnetism in CuTe₂O₅.     

Effect of solvent nature on spin exchange in rigid nitroxide biradicals

Intramolecular electron spin exchange as a function of temperature and solvent viscosity and polarity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two rigid nitroxide biradicals existing in one spatial conformation only. Temperature variations of the isotropic hyperfine splitting constanta and exchange integral value |J/a| were measured from EPR spectra and subsequently analyzed. The interaction of polar solvent molecules with >N-O fragments of nitroxide groups led to a slight decrease of the |J/a| value with the increase of temperatureT. In contrast, the interaction of polar solvent molecules with functional groups inside the bridge resulted in a noticeable increase of |J/a| vs.T. In the last case, a coverse relationship between the values of |J/a| and the hyperfine splitting constanta has been observed for solvents with different polarity.     

Exchange-coupled pairs of Fe3+ ions in beryl

The EPR spectrum of first nearest neighbour pairs of Fe³⁺ ions substituting for Al³⁺ ions in beryl is reported. The form of the pair spin Hamiltonian is discussed, and operator equivalent factors for fourth-order terms are tabulated. The Fe³⁺ pair interionic coupling corresponds to isotropic antiferromagnetic exchange with J = + 1.7 cm^-1 plus anisotropic dipolar coupling. The pair value of the zero-field splitting parameter D is + 0.0206 cm^-1 and shows a substantial shift from the single-ion value. It is proposed that resonance lines previously attributed to Fe³⁺ ions in Be²⁺ or Si⁴⁺ sites are due to Fe³⁺ pairs.     

Temperature-induced changes in the EPR spectrum of the magnetic center in kaolin

Studies of kaolin have revealed an effect characterized by an unusual temperature-induced change of the EPR spectrum of the Fe3+ ion, which is the magnetic probe in kaolin-clay. At low temperature (T=4.2 K) a resonance line with an effective g-value g1=4.13 +/- 0.16 is observed. At high temperature (T=288 K) one observes a resonance line with the effective g-value g2=2.15 +/- 0.1. The transition from the low- to high-temperature spectrum is gradual and it is accompanied by a redistribution of the absorption intensity. The observed properties of the temperature dependence of the EPR spectrum are characteristic of systems with a multiminimum potential.     

An EPR study of solid solutions of ferric oxide in γ-Al2O3

The EPR spectra of solid solutions of ferric oxide in γ-alumina have been studied. The dilute samples show two different spectra which are attributed to isolated ferric ions in the A and B sites of the spinel lattice. From the intensity dependence of the spectra on the iron concentration an approximate value of the range of the exchange forces is deduced. The concentrated samples show an isotropic spectrum at g = 2·033 which is attributed to clusters of ferric ions coupled by exchange. The temperature dependence of the intensity of the associated ions spectrum is attributed to the increase of the average spin value of the clusters with T.     

Searching for the Exchange Shift: a Set of Test Systems

We suggest that intramolecular exchange coupling J in solutions can possibly be measured with just a ruler using an analogue of the nuclear magnetic resonance paramagnetic shift. If one of the two coupled electron spins is rapidly relaxing, the resulting electron paramagnetic resonance (EPR) spectrum of the system is the resolved spectrum for the second spin with a shifted g-factor. The amount and the sense of the shift are both linear in J, which thus can be obtained from the measured shift by simple algebra. We prepared a set of complexes of rare-earth ions with nitroxides to probe this idea, but the sought effect was not yet found indicating J < 0.1 cm⁻¹ for these systems. Either the radical centers should be brought closer to the central lanthanide ion, or the ion itself should be substituted for a rapidly relaxing transition-metal ion, e.g., Cr²⁺ or Co²⁺. Furthermore we report evolving EPR spectra that reflect the inner life of the complexes in solution. Authors' address: Dmitri Stass, Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, 630090 Novosibirsk, Russia     

Spin-spin interaction of Dy3+ ions in KY(WO4)2

The spin-spin interaction of Dy³⁺ ions in a KY(WO₄)₂ single crystal is investigated by electron paramagnetic resonance (EPR) spectroscopy at a temperature of 4.2 K and a frequency of 9.2 GHz. The EPR spectra of ion pairs located in different coordination shells are analyzed. It is revealed that the considerable contribution to the spin-spin interaction of the nearest neighbor ion pair nn is made not only by the magnetic dipole-dipole interaction but also by the isotropic exchange interaction with the parameter I _nn = (+601 ± 17) × 10^?4cm^?1. The exchange interaction in pairs of more widely spaced ions is substantially weaker: I _5n = (?38 ± 3) × 10^?4cm^?1 and I _9n = (+18 ± 4) × 10^?4cm^?1. For the other ion pairs, the magnetic dipole-dipole interaction dominates. It is found that the EPR spectra of single ions and ion pairs exhibit a superhyperfine structure associated with tungsten nuclei.     

Temperature dependence of exchange integrals in magnetic insulators with Jahn-Teller ions

The exchange interaction in magnetic insulators with Jahn-Teller ions (Cu²⁺, Mn³⁺ etc.) is discussed on the basis of degenerate Hubbard model with phonons. It is shown that the interaction with a phonon mode lifting degeneracy modifies exchange and results, in particular, in reduction of exchange integrals with increasing temperature. This may account for the temperature dependence of exchange integrals, observed experimentally in K₂CuCl₄.2H₂O and in similar compounds.     

Extraordinary Magnetic Properties of Ca1–xEuxS and Sr1–xEuxS Solid Solutions

The electron paramagnetic resonance (EPR) spectra and the stationary magnetic susceptibility are investigated for Ca_1–x Eu _x S and Sr_1–x Eu _x S solid solutions (0.00005 < x < 0.0032). The EPR spectrum of Eu²⁺ in both matrices contains a wide structureless line in addition to the narrow lines of the superfine structure characteristic of ions with high local symmetry. Because of the extraordinary temperature dependence of this line in CaS:Eu, it is associated with strongly interacting magnetic centers, namely, exchange-coupling pairs and chains or more complex clusters of magnetic ions. At the same time, the dependence of the stationary magnetic susceptibility in the temperature range 4.2–50 K has no peculiarities for CaS:Eu and SrS:Eu and obeys the Curie law.     

The Temperature Dependence of Nitroxide Spin–Label Interaction Parameters: a High-Field EPR Study of Intramolecular Motional Contributions

High-field W-band electron paramagnetic resonance (EPR) spectroscopy was utilized to study the temperature dependence of the magnetic interaction parameters (g-, hyperfine-, quadrupole tensors) of two types of doublet-state nitroxide spin probes in glass-forming ortho-terphenyl solution: a five-membered ring system of pyrroline type (model for the commonly used methane thiosulfonate spin label) and a six-membered ring system of piperidine type (model for the commonly used TOAC spin label). The analysis of the g- and hyperfine tensors in terms of their isotropic and anisotropic parts reveals at least two mechanisms of motion that are responsible for the temperature dependence of the interaction parameters. The first mechanism is attributed to the overall small-angle motion of the nitroxide molecule in the glassy matrix; it leads to an averaging of the anisotropies of the EPR parameters. The second mechanism originates in an intramolecular out-of-plane motion of oxygen in the nitroxide group. This type of motion is evidenced by comparing the experimental findings for the spin-interaction parameters with the results of density functional theory calculations. The harmonic oxygen out-of-plane vibrations result in a variation of both the isotropic and anisotropic parts of the g- and hyperfine tensors. In contrast, the quadrupole tensor is not influenced by this vibration mechanism in the temperature range under study (90–240 K). Consequences of the applicability of such typical nitroxide radicals for probing details of their protein environment and for studying librational dynamics in frozen solutions are discussed.     

Features of spin exchange in nitroxide biradicals in the ionic liquid bmimPF<Subscript>6</Subscript>

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) for various nitroxide biradicals as a function of temperature and the nature of the connecting bridge between two >NO^· centers. Temperature variations of the isotropic nitrogen hyperfine splitting constant a and exchange integral values |J/a| were measured from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rigid and flexible biradicals dissolved in the ionic liquid bmimPF₆ was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in ionic liquid were observed and explained as a result of the specific intramolecular conformational transitions. The first example of a rather rigid biradical molecule becoming flexible under the influence of an ionic liquid is reported.     

强耦合的动力学Jahn-Teller效应理论

本文讨论了强耦合情况的、即电子的静态畸变能量大于晶格或分子振动量子能量的情况的动力学Jahn-Teller效应。我们发展了一种适用于强耦合情况的微扰方法,在其中将本征值及本征函数依照电子振动耦合系数的倒数或振动量子能量与静态畸变能量之比展开成幂级数,具体讨论了O_h点群中的Г₈态,求得了电子振动能级。区别于弱耦合情况的特点主要在于:1)虽然并不发生静态畸变,但是振动模的简并性及频谱却都发生了变化;2)如果与电子相耦合的振动模是“调谐”的,则电子及晶格振动的集体运动模将出现,这个理论能被用来解释Weinstock等人所做的关于TcF₆及ReF₆的红外光谱以及Raman光谱的实验结果。     

EPR and optical absorption spectra of VO2+ ions in calcium oxalate monohydrate single crystals

Abstract

Electron paramagnetic resonance (EPR) and Optical absorption spectra of vanadyl ions in calcium oxalate monohydrate single crystals have been studied. EPR spectrum at room temperature exhibits an isotropic octet spectrum. The detailed EPR analysis indicates that vanadyl ions exhibit liquid like behaviour. EPR spectrum has been studied at different temperatures. It is found that at 255 K, the EPR spectrum completely disappears. The optical absorption spectrum exhibits three absorption bands characteristic of vanadyl ions in tetragonal symmetry. From the optical data, the crystal field and tetragonal parameters have been evaluated.